CN109553574B - Pyridine acid compound, preparation method thereof, herbicide composition and application thereof - Google Patents

Pyridine acid compound, preparation method thereof, herbicide composition and application thereof Download PDF

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CN109553574B
CN109553574B CN201811609165.3A CN201811609165A CN109553574B CN 109553574 B CN109553574 B CN 109553574B CN 201811609165 A CN201811609165 A CN 201811609165A CN 109553574 B CN109553574 B CN 109553574B
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CN109553574A (en
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尚丽霞
路军
刘明杰
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Beijing Nutrichem Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • C07D213/803—Processes of preparation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
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  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention relates to the field of herbicides, and particularly discloses a pyridine acid compound, a preparation method thereof, a herbicide composition containing the pyridine acid compound as an active ingredient, and an application of the herbicide composition. The structure of the pyridine acid compound is shown as a formula (1). The invention can provide a novel pyridine acid compound which has an obvious effect of preventing and controlling weeds and is high in safety to crops.

Description

Pyridine acid compound, preparation method thereof, herbicide composition and application thereof
Technical Field
The invention belongs to the field of herbicides, and particularly relates to a pyridine acid compound, a preparation method thereof, a herbicide composition containing the pyridine acid compound as an active ingredient, and an application of the herbicide composition.
Background
The weeds in the paddy field mainly comprise grassy weeds such as barnyard grass, moleplant seeds and digitaria sanguinalis, broadleaf weeds such as dayflower, lotus grass and sedge, and sedge weeds such as cyperus rotundus and cyperus rotundus, and the weeds are mixed, have high generation density and are difficult to control.
At present, methods for controlling weeds in paddy fields are divided into a sealing treatment and a stem and leaf spray treatment, and the stem and leaf spray control of these weeds is the main means. However, the weeds have certain resistance to conventional medicaments such as quinclorac, penoxsulam, metamifop and the like, the control difficulty is increased, and the control cost is increased.
Therefore, there is a need to find a novel herbicide which has an excellent weed control effect and is highly safe when used for controlling field crops.
Disclosure of Invention
The invention aims to provide a novel pyridine acid compound which has an obvious effect of preventing and controlling weeds and is high in safety to crops.
In order to achieve the above objects, one aspect of the present invention provides a pyridine acid compound having a structure represented by formula (1) or an agrochemically acceptable salt, hydrate and solvate thereof,
Figure BDA0001924289970000011
in the formula, R1Is CN, CF3Or CCl3；R2And R3Each independently is halogen.
In a second aspect, the present invention provides a process for preparing a pyridine acid compound having a structure represented by the above formula (1), which comprises the steps of,
1) carrying out a first coupling reaction on a compound with a structure shown in a formula (2) and a compound with a structure shown in a formula (3) in the presence of a first base to obtain a compound with a structure shown in a formula (4);
2) carrying out a second coupling reaction on the compound with the structure shown in the formula (4) and the compound with the structure shown in the formula (5) in the presence of a second base to obtain a compound with the structure shown in the formula (6);
3) decarboxylating the compound with the structure shown in the formula (6) to obtain the pyridine acid compound with the structure shown in the formula (1),
Figure BDA0001924289970000021
in the formula, R1、R2And R3As defined above, A represents halogen and B represents a carboxyl protecting group.
The third aspect of the present invention provides a herbicidal composition containing, as an active ingredient, a pyridine acid compound having a structure represented by the above formula (1) or an agrochemically acceptable salt, hydrate or solvate thereof.
In a fourth aspect, the present invention provides the use of the above herbicide composition for the control of annual and perennial grassy weeds and broadleaf weeds.
The pyridine acid compound provided by the invention has obvious excellent safety for field crops on the premise of ensuring excellent control effect on weeds in the field crops. Particularly, the pyridine acid compound provided by the invention has better safety to crops such as wheat, corn, rice, rape and the like.
In addition, the method for preparing the pyridine acid compound is simple and low in cost.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, the "halogen" includes fluorine, chlorine, bromine or iodine.
In a first aspect, the present invention provides a pyridine acid compound having a structure represented by formula (1) or an agrochemically acceptable salt, hydrate or solvate thereof,
Figure BDA0001924289970000031
in the formula, R1Is CN, CF3Or CCl3；R2And R3Each independently is halogen.
Preferably, R2And R3Each independently F or Cl.
More preferably, the pyridine acid compound has a structure shown in a formula (1-1) to a formula (1-10),
Figure BDA0001924289970000032
Figure BDA0001924289970000041
Figure BDA0001924289970000051
in a second aspect, the present invention provides a process for preparing a pyridine acid compound having a structure represented by the above formula (1), which comprises the steps of,
1) carrying out a first coupling reaction on a compound with a structure shown in a formula (2) and a compound with a structure shown in a formula (3) in the presence of a first base to obtain a compound with a structure shown in a formula (4);
2) carrying out a second coupling reaction on the compound with the structure shown in the formula (4) and the compound with the structure shown in the formula (5) in the presence of a second base to obtain a compound with the structure shown in the formula (6);
3) decarboxylating the compound with the structure shown in the formula (6) to obtain the pyridine acid compound with the structure shown in the formula (1),
Figure BDA0001924289970000052
in the formula, R1、R2And R3As defined above, A represents halogen and B represents a carboxyl protecting group.
According to the present invention, B in the formula (2) is a carboxyl protecting group which is a variety of groups commonly used in the art for protecting carboxyl groups, and may be, for example, benzyl.
Specific examples of the compound of the formula (2) include the following compounds:
formula (2-1): in the formula (2), R3A compound wherein F, B is benzyl;
formula (2-2): in the formula (2), R3Is a compound of Cl and B being benzyl; and the like.
A in the formula (3) is halogen, preferably F, Cl, Br or I, more preferably F or Cl.
Specific examples of the compound of the formula (3) include the following compounds:
formula (3-1): a compound of formula (3) wherein A is F;
formula (3-2): a compound of formula (3) wherein A is Cl; and the like.
A first coupling reaction of a compound with a structure shown in a formula (2) and a compound with a structure shown in a formula (3) is carried out in the presence of the first base, wherein the first base can be an inorganic base or an organic base, and preferably, the first base is one or more of sodium methoxide, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide and triethylamine; more preferably, the first base is sodium methoxide and sodium carbonate.
The molar amount of compound of formula (2) and compound of formula (3) may vary within wide limits, preferably the molar ratio of compound of formula (2) and compound of formula (3) is 1: 1.01-2; more preferably, the compound of the structure represented by the formula (2) and the compound of the structure represented by the formula (3) are used in a molar ratio of 1: 1.05-1.5.
In addition, the compound of the structure represented by formula (2) and the first base may be used in a molar ratio of 1: 1.01-2; preferably, the compound having the structure shown in the formula (2) and the first base are used in a molar ratio of 1: 1.05-1.5.
Preferably, the first contact reaction is carried out in the presence of a solvent which is a variety of organic solvents that do not react with the reactant and that can dissolve the reactant, and examples of such solvents include: one or more of dimethylsulfoxide, N-dimethylformamide, tetrahydrofuran, toluene, dichloromethane, chloroform, chlorobenzene, and acetonitrile.
The amount of the organic solvent to be used may be selected depending on the reactants, and for example, 2 to 10 moles of the organic solvent may be used based on 1mole of the compound having the structure represented by formula (2).
Preferably, the reaction conditions of the first contact reaction include: the reaction temperature is 80-170 ℃ and the reaction time is 3-12 hours.
After the first contact reaction is completed, the first contact product may be purified according to a purification method conventional in the art, and for example, the first contact product may be neutralized with an acid (for example, hydrochloric acid may be used) and then extracted with an organic solvent (for example, diethyl ether may be used).
According to the present invention, a compound having a structure represented by formula (6) is obtained by subjecting a compound having a structure represented by formula (4) and a compound having a structure represented by formula (5) to a second coupling reaction in the presence of a second base.
Specific examples of the compound of the formula (4) include the following compounds:
formula (4-1): in the formula (2), R3Compound wherein F, A is F, B is benzyl;
formula (4-2): in the formula (2), R3Is Cl, A is F, B is benzyl;
formula (4-3): in the formula (2), R3F, A is Cl and B is benzyl;
formula (4-4): in the formula (2), R3Is a compound of Cl, A is Cl and B is benzyl; and the like.
A in the formula (3) is halogen, preferably F, Cl, Br or I, more preferably F or Cl.
Specific examples of the compound of the formula (5) include the following compounds:
formula (5-1): in the formula (3), R1Is CN, R2A compound that is F;
formula (5-2): in the formula (3), R1Is CF3、R2A compound that is F;
formula (5-3): in the formula (3), R1Is CCl3、R2A compound that is F;
formula (5-4): in the formula (3), R1Is CN, R2A compound that is Cl;
formula (5-5): in the formula (3), R1Is CF3、R2A compound that is Cl;
formula (5-6): in the formula (3), R1Is CCl3、R2A compound that is Cl; and the like.
The second base may be any of various organic or inorganic bases generally used in the art, preferably an inorganic base, more preferably one or more of sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide, and further preferably sodium carbonate.
The molar amount of compound of formula (4) and compound of formula (5) may vary within wide limits, preferably the molar ratio of compound of formula (4) and compound of formula (5) is 1: 1.01-2; more preferably, the compound of the structure represented by formula (4) and the compound of the structure represented by formula (5) are used in a molar ratio of 1: 1.05-1.5.
In addition, the compound of the structure represented by formula (4) and the second base may be used in a molar ratio of 1: 1.01-2; preferably, the compound having the structure represented by formula (4) and the second base are used in a molar ratio of 1: 1.05-1.5.
Preferably, the second contact reaction is carried out in the presence of a solvent which is a variety of organic solvents that do not react with the reactant and that can dissolve the reactant, and examples of such solvents include: one or more of xylene, toluene, dichloromethane, dichloroethane, chloroform, and chlorobenzene.
The amount of the organic solvent to be used may be selected depending on the reactants, and for example, 2 to 10 moles of the organic solvent may be used based on 1mole of the compound having the structure represented by formula (4).
Preferably, the reaction conditions of the second contact reaction include: the reaction temperature is 80-170 ℃ and the reaction time is 3-12 hours.
After the second contact reaction is completed, the second contact product may be purified according to a purification method conventional in the art, and for example, the second contact product may be neutralized with an acid (for example, hydrochloric acid may be used) and then concentrated.
According to the present invention, a pyridine-based compound having a structure represented by formula (1) is obtained by decarboxylating a compound having a structure represented by formula (6) to form a protecting group. The method for removing the protecting group may be selected depending on the carboxyl protecting group to be used, and for example, when the carboxyl protecting group is a benzyl group (Bn), the compound having the structure represented by formula (5) may be reduced with hydrogen to obtain the pyridine-based compound having the structure represented by formula (1).
The above-mentioned hydrogen reduction may be carried out in the presence of various catalysts generally used in the art, for example, in the presence of palladium on carbon. The palladium on carbon and hydrogen may be used in an amount conventional in the art, for example, in an amount of 2 to 5 moles with respect to 1mole of the compound having the structure represented by formula (6).
The reduction reaction is preferably carried out in the presence of an organic solvent, and toluene may be used as such an organic solvent. After the reaction, purification may be carried out according to a purification method which is conventional in the art, and will not be described herein again.
In a third aspect, the present invention also provides a herbicidal composition containing, as an active ingredient, a pyridine acid compound having a structure represented by the above formula (1) or an agrochemically acceptable salt, hydrate or solvate thereof.
The content of the active ingredient in the herbicidal composition of the present invention may vary within a wide range, and specifically, the content of the active ingredient in the composition is 1 to 95% by weight, preferably 5 to 80% by weight, more preferably 6 to 50% by weight.
In the herbicidal composition of the present invention, the herbicidal composition usually contains an agriculturally pharmaceutically acceptable surfactant and a carrier in addition to the active ingredient.
The surfactant may be any of various surfactants known in the field of pesticide formulation, and one or more of an emulsifier, a dispersant and a wetting agent are preferred in the present invention.
The carrier other than the surfactant may be any of various carriers known in the field of pesticide formulation, including various silicates, carbonates, sulfates, oxides, phosphates, plant carriers, and synthetic carriers. Specifically, for example: the carrier can be one or more of white carbon black, kaolin, diatomite, clay, talc, organic bentonite, pumice, titanium dioxide, dextrin, cellulose powder, light calcium carbonate, soluble starch, corn starch, sawdust powder, urea, amine fertilizer, a mixture of urea and amine fertilizer, glucose, maltose, sucrose, anhydrous potassium carbonate, anhydrous sodium carbonate, anhydrous potassium bicarbonate, anhydrous sodium bicarbonate, attapulgite, a mixture of anhydrous potassium carbonate and anhydrous potassium bicarbonate and a mixture of anhydrous sodium carbonate and anhydrous sodium bicarbonate.
The emulsifier may be any of various emulsifiers known in the field of pesticide formulation, and specifically, the emulsifier may be one or more of calcium dodecylbenzenesulfonate, trisethylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene polyoxypropylene ether, fatty amine, ethylene oxide adduct of fatty amide, fatty acid polyoxyethylene ester, rosin acid ethylene oxide adduct, polyol fatty acid ester and ethylene oxide adduct thereof, styrylphenyl polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, hydroxyl-terminated polyoxyethylene polyoxypropylene ether, styrylphenol formaldehyde resin, polyoxyethylene polyoxypropylene ether, and castor oil polyoxyethylene ether.
The dispersant can be various dispersants known in the field of pesticide formulation, and specifically, the dispersant can be one or more of acrylic acid homopolymer sodium salt, maleic acid disodium salt, naphthalene sulfonic acid formaldehyde condensate sodium salt, rosin block polyoxyethylene ether polyoxypropylene ether sulfonate, hydroxyl-terminated polyoxyethylene polyoxypropylene ether block copolymer, tristyrylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate, p-hydroxyphenyl lignosulfonate sodium salt and calcium lignosulfonate.
The wetting agent can be various wetting agents known in the field of pesticide formulation, and specifically, the wetting agent can be one or more of sodium dodecyl sulfate, secondary alkyl sodium sulfate, sodium dodecyl benzene sulfonate, fatty alcohol-polyoxyethylene ether, alkyl naphthalene sulfonate and alkylphenol resin polyoxyethylene ether sulfate.
The herbicide composition can also contain various preparation additives commonly used in the field of pesticide formulations, and specifically, the preparation additives can be one or more of solvents, cosolvents, thickeners, antifreezes, capsule wall materials, protective agents, antifoaming agents, disintegrants, stabilizers, preservatives and binders.
The solvent may be any of various solvents known in the field of pesticide formulation, and specifically, the solvent may be one or more of an organic solvent, a vegetable oil, a mineral oil, a solvent oil and water.
Wherein the organic solvent comprises one or more of N-methylpyrrolidone, tetrahydrofuran, dimethyl sulfoxide, N-dimethyldecanamide, N-dimethylformamide, trimethylbenzene, tetramethylbenzene, xylene, toluene, octane, heptane, methanol, isopropanol, N-butanol, tetrahydrofurfuryl alcohol, tributyl phosphate, 1, 4-dioxane and cyclohexanone.
The vegetable oil comprises one or more of methylated vegetable oil, rosin-based vegetable oil, turpentine, epoxidized soybean oil, peanut oil, rapeseed oil, castor oil, corn oil and pine seed oil.
The mineral oil comprises one or more of liquid wax, engine oil, kerosene and lubricating oil.
Meanwhile, the solvent can also be used as a cosolvent.
The antifreeze can be various antifreeze agents known in the field of pesticide formulation, and the invention is preferably one or more of ethylene glycol, propylene glycol, glycerol and urea.
The thickener can be various thickeners known in the field of pesticide formulation, and specifically can be one or more of xanthan gum, polyvinyl alcohol, polypropylene alcohol, polyethylene glycol, white carbon black, diatomite, kaolin, clay, sodium alginate, magnesium aluminum silicate, sodium aluminum silicate, carboxymethyl cellulose, sodium hydroxypropyl cellulose and organic bentonite.
The capsule wall material can be various capsule wall materials known in the field of pesticide formulation, and the invention is preferably polyurethane, polyurea or urea resin.
The protective agent may be any of various protective agents known in the field of pesticide formulation, and polyvinyl alcohol and/or polyethylene glycol is preferred in the present invention.
The defoaming agent may be any of those known in the field of agricultural agent formulation, and in the present invention, one or more of organosiloxane, tributyl phosphate and silicone are preferable.
The stabilizer is one or more selected from triphenyl phosphite, epichlorohydrin and acetic anhydride.
The antiseptic is selected from one or more of benzoic acid, sodium benzoate, 1, 2-benzisothiazolin-3-one (BIT), Kathon and potassium sorbate.
According to the present invention, the formulation of the herbicide composition may be various formulations commonly used in the art, for example, the formulation of the herbicide composition may be emulsifiable concentrate, aqueous emulsion, aqueous suspension, oil suspension, suspoemulsion, dispersible oil suspension, wettable powder, soluble powder, water dispersible granule or soluble granule. Wettable powders are preferred. The above formulations can be prepared by methods conventional in the art.
Preferably, the missible oil preparation comprises 1-95% of active ingredients, 0-20% of cosolvent, 1-30% of emulsifier and the balance of solvent to 100% by weight.
The preparation method of the emulsifiable concentrate preparation can comprise, for example, mixing and stirring the active components, the solvent, the cosolvent and the emulsifier to form a uniform transparent oil phase, so as to obtain the emulsifiable concentrate preparation.
Preferably, the missible oil preparation comprises 1-95% of active ingredients, 0-20% of cosolvent, 1-30% of emulsifier and the balance of solvent to 100% by weight.
The preparation method of the emulsifiable concentrate preparation can comprise, for example, mixing and stirring the active components, the solvent, the cosolvent and the emulsifier to form a uniform transparent oil phase, so as to obtain the emulsifiable concentrate preparation.
Preferably, the aqueous emulsion or microemulsion comprises, by weight, 1-95% of an active ingredient, 1-30% of an emulsifier, 0-30% of a cosolvent, 1-30% of a solvent, 0-10% of an antifreeze, 0-10% of a thickener, and the balance of water to 100%.
Preferably, the preparation method of the aqueous emulsion can comprise the steps of mixing the active ingredients, the emulsifier, the cosolvent and the solvent to form a uniform oil phase; mixing water, thickener, antifreeze, etc. to obtain uniform water phase. Under high-speed shearing, adding the water phase into the oil phase or adding the oil phase into the water phase to form the aqueous emulsion with good dispersibility.
Preferably, the microemulsion is prepared by mixing and stirring the active ingredient, the emulsifier and the solvent into a uniform and transparent oil phase. Under stirring. Water was added gradually to form a uniform, transparent microemulsion.
Preferably, the water suspension agent comprises 1-95% of active ingredients, 1-30% of surfactant, 1-10% of antifreeze agent, 0.1-5% of thickening agent and the balance of water to 100% by weight.
Preferably, the oil suspending agent comprises 1-95% of active ingredients, 1-30% of emulsifying agents, 0.1-10% of dispersing agents, 0.1-5% of thickening agents and oil to 100% of the total weight.
The preparation method of the water/oil suspending agent comprises the following steps: water or oil is used as a medium, active components such as surfactant, auxiliary agent and the like are added into a sanding kettle, and after being ground to a certain particle size, the active components are filtered. And adding the weighed thickening agent into the ground mother liquor, and uniformly shearing and dispersing. Making into oil suspension or water suspension.
Preferably, the soluble granule, soluble powder, water dispersible granule or wettable powder comprises 1-95% of active ingredients, 1-30% of surfactant and the balance of other carriers to 100% by weight.
The preparation method of the water dispersible granule and the soluble granule comprises the following steps: the active components, the dispersing agent, the wetting agent, the carrier and the like are uniformly mixed, then are crushed to a certain particle size through air flow, are added with water for kneading, and finally are added into a granulator for granulation, and the water dispersible granules or the soluble granules can be obtained after drying.
The preparation method of the soluble powder and the wettable powder comprises the following steps: mixing the active components, various adjuvants and other fillers, and pulverizing with superfine pulverizer.
Preferably, the microcapsule suspension comprises, by weight, 1-95% of an active ingredient, 1-30% of a solvent, 0.1-5.0% of a protective agent, 0.05-1.0% of a defoaming agent, 1-30% of a capsule wall material, 1-30% of a dispersing agent, 0-30% of a wetting agent, 0-10% of an antifreezing agent, 0.1-5% of a thickening agent, and water to make up to 100%.
The preparation method comprises the following steps: mixing the solvent and the capsule wall material, and then adding the active ingredients; then adding the mixture into a mixture consisting of a protective agent, an antifreezing agent, a defoaming agent and water for emulsification, and stirring until the polymerization reaction is finished; then adding a thickening agent, a dispersing agent and a wetting agent to obtain the stable microcapsule suspending agent.
In a fourth aspect, the present invention provides the use of the above herbicide composition for controlling annual and perennial grassy weeds and broadleaf weeds.
The weeds can be one or more of alopecurus, bluegrass, crabgrass, barnyard grass, semen Euphorbiae, cardamine hirsute, descurainia sophia, cleavers, maidenhair, Amaranthus retroflexus, green beefsteak, eclipta prostrata, arrowhead and abnormal-shaped cyperus.
The herbicidal compositions of the present invention may be provided in the form of a finished formulation, i.e., the individual materials in the composition have been mixed; or in separate formulations which are self-mixing in a tub or tank prior to use and optionally diluted by mixing with water depending on the concentration of active desired.
The compositions of the present invention may also be used in admixture with other compounds having fungicidal, insecticidal or herbicidal properties, as well as with nematicides, protectants, growth regulators, plant nutrients or soil conditioners.
According to the present invention, the specific application method of the herbicide composition is generally to apply the herbicide composition of the present invention to crops and the places where the crops grow, before or after the weeds germinate, according to a conventional method. The application method can be soil sealing, stem leaf spraying and the like, and is simple. The herbicide composition of the invention is preferably subjected to soil sealing treatment after sowing and before emergence, and can prevent and remove emerged weeds and unearthed weeds. The application rate of the herbicide composition provided by the invention depends on weather conditions or crop conditions, and the herbicide composition is usually 10-500g/hm in active ingredient content2Preferably in the range of 20 to 200g/hm2More preferably 20-100g/hm2Is administered. The application rate of the herbicidal compositions provided by the present invention is also dependent on external factors such as climate.
The application rate of the herbicide composition provided by the invention can reduce the influence of climate by using a proper formulation.
The present invention will be further described with reference to specific examples, but the present invention is not limited to the examples.
In the following examples, nuclear magnetic data was measured using model AVANCE III HD 500 of brueck, and mass spectral data was measured using model 6120 of Agilent.
A pyridine-based compound having a structure represented by formula (1) was synthesized according to the following synthetic route.
Figure BDA0001924289970000141
Example 1: synthesis of 3-chloro-6- (4- (4-cyano-2-fluorophenoxy) phenoxy) pyridine acid
Phenyl 3-chloro-6-hydroxypicolinate (31.57g, 0.12mole) and p-dichlorotoluene (14.6g, 0.1mole) were dissolved in 200ml of a dimethyl sulfoxide solution, and sodium methoxide (64.81g, 0.12mole) and sodium carbonate (10.60g,0.12mole) were added thereto, and the temperature was raised to 110 ℃ for 12 hours until the reaction was completed. After the reaction was completed and the temperature was decreased, neutralized with hydrochloric acid, extracted with ether, the organic phase was collected and concentrated under reduced pressure to give intermediate 3-chloro-6- (4-chlorophenoxy) pyridine-2-2-phenylacetate (31.0g, 0.08mole, yield 83%). Redissolving the intermediate in 100ml xylene solvent, adding potassium carbonate (13.82g, 0.1mole) and 3-fluoro-4-hydroxybenzonitrile (13.71g, 0.1mole), heating to 100 ℃, controlling the temperature for 12 hours, reducing the temperature after the reaction is finished, neutralizing with hydrochloric acid, washing with water, evaporating the solvent for separation to obtain 3-chloro-6- (4- (4-cyano-2-fluorophenoxy) phenoxy) pyridine acid ester (33.24g, 0.07mole), hydrogenating in toluene solution by taking Pd/C as a catalyst, filtering and separating solid after the reaction is finished, and performing desolventizing column chromatography to obtain 3-chloro-6- (4- (4-cyano-2-fluorophenoxy) phenoxy) pyridine acid (21.54g, 0.05 mole).
Example 2: preparation of 3-chloro-6- (4- (4-cyano-2-chlorophenoxy) phenoxy) pyridine acid
3-chloro-4-hydroxybenzonitrile was used instead of 3-fluoro-4-hydroxybenzonitrile in example 1 to give 3-chloro-6- (4- (4-cyano-2-fluorophenoxy) phenoxy) picolinic acid (20.06g, 0.05 mole).
Example 3: preparation of 3-chloro-6- (4- (2-fluoro-4- (trifluoromethane) phenoxy) pyridine acid
3-chloro-6- (4- (2-fluoro-4- (trifluoromethane) phenoxy) pyridine acid (17.11g, 0.04mole) was obtained by substituting 2-fluoro-4- (trifluoromethane) phenol for 3-fluoro-4-hydroxybenzonitrile in example 1.
Example 4: preparation of 3-chloro-6- (4- (2-chloro-4- (trifluoromethyl) phenoxy) pyridine acid
3-chloro-6- (4- (2-chloro-4- (trifluoromethyl) phenoxy) pyridine acid (24.43g, 0.055mole) was obtained by substituting 2-chloro-4- (trifluoromethyl) phenol for 3-fluoro-4-hydroxybenzonitrile in example 1.
Example 5: preparation of 3-chloro-6- (4- (2-chloro-4- (trichloromethyl) phenoxy) pyridine acid:
3-chloro-6- (4- (2-chloro-4- (trichloromethyl) phenoxy) picolinic acid (25.17g, 0.051mole) was obtained by substituting 2-chloro-4- (trichloromethyl) phenol for 3-fluoro-4-hydroxybenzonitrile in example 1.
Example 6: preparation of 3-chloro-6- (4- (2-fluoro-4- (trifluoromethane) phenoxy) pyridine acid
3-chloro-6- (4- (2-fluoro-4- (trifluoromethane) phenoxy) pyridine acid (28.67g, 0.06mole) was obtained by substituting 2-fluoro-4- (trichloromethyl) phenol for 3-fluoro-4-hydroxybenzonitrile in example 1.
Example 7: preparation of 6- (4- (4-cyano-2-fluorophenoxy) phenoxy) -3-fluoropyridinic acid
Phenyl-3-fluoro-6-hydroxypyridinate instead of phenyl 3-chloro-6-hydroxypyridinate in example 1, 6- (4- (4-cyano-2-fluorophenoxy) phenoxy) -3-fluoropyridinic acid (25.76g, 0.07mole) was prepared.
Example 8: preparation of 6- (4- (2-chloro-4-cyanophenoxy) phenoxy) -3-fluoropyridinic acid
Preparation of 6- (4- (2-chloro-4-cyanophenoxy) phenoxy) -3-fluoropyridinic acid (19.24g, 0.04mole) was prepared by substituting phenyl-3-fluoro-6-hydroxypyridinate for phenyl 3-chloro-6-hydroxypyridinate in example 1 and 3-chloro-4-hydroxybenzonitrile for 3-fluoro-4-hydroxybenzonitrile in example 1.
Example 9: preparation of 3-fluoro-6- (4- (2-fluoro-4- (trifluoromethyl) phenoxy) pyridine acid
Preparation of 3-fluoro-6- (4- (2-fluoro-4- (trifluoromethyl) phenoxy) pyridine acid (16.45g, 0.04mole) was prepared by substituting phenyl-3-fluoro-6-hydroxypyridinate for phenyl 3-chloro-6-hydroxypyridinate in example 1 and 2-fluoro-4- (trifluoromethyl) phenol for 3-fluoro-4-hydroxybenzonitrile in example 1.
Example 10: preparation of 6- (4- (2-chloro-4- (trifluoromethyl) phenoxy) -3-fluoropyridinic acid
Preparation of 6- (4- (2-chloro-4- (trifluoromethyl) phenoxy) -3-fluoropyridinic acid (19.08g, 0.04mole) was prepared by substituting phenyl-3-fluoro-6-hydroxypyridinate for phenyl 3-chloro-6-hydroxypyridinate in example 1 and 2-chloro-4- (trifluoromethyl) phenol for 3-fluoro-4-hydroxybenzonitrile in example 1.
The structures of the compounds obtained in examples 1 to 10 and the nuclear magnetic and mass spectrometric data thereof are shown in Table 1.
TABLE 1
Figure BDA0001924289970000161
Figure BDA0001924289970000171
Test example 1
The herbicidal activity of the compounds of the present invention was tested by the indoor bioactivity assay below.
The test method is as follows:
the test adopts a greenhouse potting method, seeds of wheat, corn, rice, rape, alopecurus (gramineae weeds), bluegrass (gramineae weeds), crabgrass (gramineae weeds), barnyard grass (gramineae weeds), moleplant seeds (gramineae weeds), cardamine (broad leaf weeds), descurainia sophia (broad leaf weeds), cleavers (broad leaf weeds), malpigweed (broad leaf weeds), amaranthus retroflexus (broad leaf weeds), big green (broad leaf weeds), eclipta (broad leaf weeds), arrowhead (broad leaf weeds) and cyperus rotundus (cyperaceae weeds) are respectively forced to germinate until the alopecuroides are exposed, the alopecurus seeds are put into a small flowerpot filled with 3/5 culture soil (field soil: vermiculite: 3:1:1) by using a hook brush pen, 6 × 6 alopecuroides are sown in each pot, and the pot is covered with soil for 0.2-0.5 cm.
Adding water into the tray with the small flowerpot, and pouring out the excessive water in the tray after the culture soil is completely soaked by the water. And then watering for 1 time every 3 days according to the soil humidity, thinning when crops and weeds grow to 2-3 true leaves and each pot keeps 15-20 seedlings with consistent growth vigor, culturing wheat, corn, rice and gramineous monocotyledonous weeds to 3-4 leaf stage and rape and broad-leaved dicotyledonous weeds to 4-6 leaf stage, dissolving the tested compound, adding a proper amount of 0.15% Tween-80 for dilution, carrying out stem and leaf spraying treatment by an ASS-5 walking type spraying tower, using 75% clopyralid acid soluble granules produced by the American Dow's Yinong company as a contrast agent, and setting clear water for treatment as a blank contrast. And transferring the liquid medicine on the leaf surfaces to a greenhouse for continuous culture and observation after the liquid medicine is dried, and investigating the activity or weeding effect of each treatment after 10-20 days.
The weeding effect calculation method comprises the following steps:
Figure BDA0001924289970000181
Figure BDA0001924289970000182
the results of the experiments are shown in tables 2 to 4, in which the compounds obtained in examples 1 to 10 are shown as 1 to 10, respectively, tables 2 and 3 show the control effects of the example compounds and the control agents on annual weeds, and table 4 shows the activities of the example compounds and the control agents on crops.
TABLE 2
Figure BDA0001924289970000191
TABLE 3
Figure BDA0001924289970000192
TABLE 4
Figure BDA0001924289970000201
Note: negative activity indicates a certain growth promoting effect.
Indoor biological activity tests show that 1-10 compounds have good activity on alopecurus, bluegrass, crabgrass, barnyard grass, semen euphorbiae, cardamine hirsute, descurainia sophia, cleavers, maica, amaranthus retroflexus, green beefsteak, eclipta prostrata, arrowheads, cyperus heterotypii and other weeds. And under the same dosage, the activity to broadleaf weeds is higher than that to grass weeds.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (20)

1. A pyridine acid compound having a structure represented by formula (1) or an agrochemically acceptable salt thereof,
Figure FDA0002476547420000011
in the formula, R1Is CN, CF3Or CCl3；R2And R3Each independently is halogen.
2. The compound of claim 1, wherein R2And R3Each independently F or Cl.
3. The compound of claim 1, wherein the pyridine acid compound has a structure represented by formula (1-1) to formula (1-10),
Figure FDA0002476547420000012
Figure FDA0002476547420000021
4. a process for producing a pyridine acid compound having a structure represented by the formula (1) according to any one of claims 1 to 3, which comprises the steps of,
1) carrying out a first coupling reaction on a compound with a structure shown in a formula (2) and a compound with a structure shown in a formula (3) in the presence of a first base to obtain a compound with a structure shown in a formula (4);
2) carrying out a second coupling reaction on the compound with the structure shown in the formula (4) and the compound with the structure shown in the formula (5) in the presence of a second base to obtain a compound with the structure shown in the formula (6);
3) decarboxylating the compound with the structure shown in the formula (6) to obtain the pyridine acid compound with the structure shown in the formula (1),
Figure FDA0002476547420000031
in the formula, R1、R2And R3As defined above, A represents halogen and B represents a carboxyl protecting group.
5. The process of claim 4, wherein the carboxyl protecting group is benzyl.
6. The process of claim 5, wherein the first base is one or more of sodium methoxide, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and triethylamine.
7. The method according to claim 5, wherein the compound of the structure represented by formula (2) and the compound of the structure represented by formula (3) are used in a molar ratio of 1: 1.01-2.
8. The method according to claim 5, wherein the compound having the structure represented by formula (2) and the first base are used in a molar ratio of 1: 1.01-2.
9. The method of claim 5, wherein the second base is one or more of sodium carbonate, potassium hydroxide, and sodium hydroxide.
10. The method according to claim 5, wherein the compound of the structure represented by formula (4) and the compound of the structure represented by formula (5) are used in a molar ratio of 1: 1.01-2.
11. The method according to claim 5, wherein the compound having the structure represented by formula (4) and the second base are used in a molar ratio of 1: 1.05-2.
12. The method according to claim 5, wherein the pyridine-based compound having a structure represented by formula (1) is obtained by reducing a compound having a structure represented by formula (5) with hydrogen in the presence of palladium on carbon.
13. A herbicidal composition, characterized in that the active ingredient of the herbicidal composition comprises a pyridine-based compound having the structure represented by the formula (1) according to any one of claims 1 to 3 or an agrochemically acceptable salt thereof.
14. A herbicidal composition according to claim 13, wherein the active ingredient is present in an amount of 1 to 95% by weight of the herbicidal composition.
15. A herbicidal composition according to claim 14, wherein the active ingredient is present in an amount of 5 to 80% by weight of the herbicidal composition.
16. A herbicidal composition according to claim 15, wherein the active ingredient is present in an amount of 6 to 50% by weight of the herbicidal composition.
17. A herbicidal composition according to claim 13, wherein the herbicidal composition further comprises an agriculturally pharmaceutically acceptable surfactant and a carrier.
18. The herbicidal composition according to any one of claims 13 to 17, wherein the herbicidal composition is in the form of emulsifiable concentrate, aqueous emulsion, aqueous suspension, oil suspension, suspoemulsion, dispersible oil suspension, wettable powder, soluble powder, water dispersible granule or soluble granule.
19. Use of a herbicidal composition according to any one of claims 13 to 18 for controlling annual and perennial grasses and broadleaf weeds.
20. The use of claim 19, wherein the weeds are one or more of alopecurus, bluegrass, crabgrass, barnyard grass, stephania japonica, cardamine, descurainia sophia, cleavers, maidenhair, amaranthus retroflexus, atriplex hortensis, eclipta prostrata, arrowheads, and cyperus heterotypii.
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